Hydrocarbon oil and process for manufacturing the same



Patented July 1 4, 1931 3 UNITEDSTATES PATENT OFF-ICE GARLAND H. B. DAVIS, 03? BATON ROUGE, LOUISIANA, ASSIGNOR TO STANDARD; OIL

DEVELOPMENT COMPANY, A QOBPORATION OF DELAWARE No Drawing. I

The present'invention relates to improved methods for the production of high grade lubricating oils and more specifically com temperatures, for example; ice machine oil and the like. There are methods at the present time for reducing the-pour point of lubrieating oils and these ordinarily consist of freezing the oil and separating the solidified paraflinic material by filtration or by centrifugal action, but these methods are extremely expensive. 3

Another highly desirable property for lubricating oils is a relatively small change in the viscosity between temperatures of say 210 .F. and 100 F. In other words, it isdesirable for the oil to .approach the Pennsylvania type of lubricating oilin which the viscosity-temperature curve is relatively fiat, rather than to approach the Texas or Colombian type of oil in which viscosity changes very rapidly with temperature change. Hereafter the. phrase high quality will be used to designate oils having the desirable relatively flat temperature-viscosity curve and low quality for oils at the other extreme, such as Texas coastal oils, irrespective of other properties usually-necessary to a superior lubricant. As used here quality is equivalent to viscosity -index as defined by v Dean and Davis in their article in Chemical and Metallurgical Engineering, vol. 36, page I have found that the presence of parafiin I or other waxy hydrocarbon materials tends to improve the quality of an oil and that the same oil after paraflin has been removed will be more or less inferior in respect to its viscosity-temperature characteristics. It is, therefore, highly desirable to keep 'solidifiable paraflinic materials in the oil from the,

- point of view of desirable temperature-viscosity characteristics, but at the same-time long aliphatic hydrocarbon chains.

HYDROGARIBON OIL AND PROCESS FOR MANUFACTURING THE SAME Application meaua a, 1930. Serial no. 449,83.

the presence of such materials is undesirable with respect to solidificationor pour points, as will be understood;

I have discovered methods by which arafin containing oils, such as those obtalned from Pennsylvania or equivalent crudes or Mid-Gontinent. crudes of the intermediate type, or even from low grade crudes, which have been improved in quality by the addition of petrolatum or paraflin wax, may be greatly improved with respect to their pour or solidification points without detriment to quality. This is likewise of particular importance with oils produced by hydrogenation of heavy carbonaceous materials, since pour points of such products are frequently high, This may be accomplished at a low cost and without expensive refrigeration methods' I have found that certain materials added to these oils have the power of depressing or otherwise reducing the pour point of the oil as determined by the standard test method given in Report on petroleum products and lubricants and methods for tests relating to petroleum products by the committee D-2 of the American Asso ciation of Testing Materials, and published in 1928. The method'appears on page 83 and the following pages of this report. 4

In the use'of my method I first chlorinate a parafiinic material such as parafiin wax, petrola-tum or other aliphatic hydrocarbons, either pure or in a mixed state, by means of passihg chlorine therethru while at a temperature between about 140 and 300 F. for a prolonged period after which it is found that the paraflin contains 10-to 12% chlorine, or more. Other materials as indicated above may be used in place of par'aflin wax and such materials are chosen which contain relatively matic hydrocarbon material such as naphthalene or anthraeene or the like is then mixed with, say an equal weight of aluminum chloride and the chlorinated oil is slowly added while; maintaining a low condensation temperature ofabout 140'to'160 F. The. proportion of the-chlorinated product to the aromatic material may vary considerably say from.10 to .50 parts of the latter to 1.0 of

9 Aro- 5 carbons may be used, for example; benzol or 50% where it is desired to improve the qualthe former. The mixture is kept in constant agitation and it. is highly desirable to have present some solvent, say a light hydrocarbon predominately saturated, such as kerosene or the like. The reaction may be carried out at room temperature and under such conditions 'oil are added to low quality oils with rela-,

it takes a somewhat longer time, say about 24 hours. It is desirable at the end of the time to raise the temperature slowly to about 200 F. to complete the reaction and through: out copious volumes of hydrochloric acid vapors are allowed to escape from the treating vessel. Instead of a solid aromatic hydrocarbon other materials rich in cyclic hydrotoluol, although in this case it is particularly desirable to carefully prevent undue rise in temperature. Aromatic gas oils such as those occurring in the California crudes and par ticular'ly tube and tank cycle stock such as is produced from. cracking crudes or gas oils are also satisfactory, particularly California cycle oil. and the like.

The oil mixture is then allowed to stand for a considerable time to allow sludge constituents to settle and the oil is withdrawn and cooled. It is preferable at this time to remove a part or all of the unreacted paraflin and this may be done by cold pressing or other similarmethods, although distillation under high vacuum is preferred. The unreacted wax is removed as a vapor, leaving thesynthetic oil as a residue. The synthetic oil may then be blended with the wax-bearing ,oil in any desirable proportion, say less than 10% or 5%, or even 1%, if it is merely desired to reduce the pour point of the paraffin containing stock, or it may be added in larger quantities, say from 10 or 20 to 30 or even to ity-of the product i. e. with respect to its viscosity-temperature characteristics. It will be found that the blended oil has a greatly reduced pour point as determined by the standard test method referred to above, even when less than 1% of the synthetic oil is added and if larger amounts of the synthetic tively steep viscosity-temperature curves it ,will be found that the blend has a viscositytemperat-ure curve, the slope of which is considerably reduced and brought nearer to the ideal type of lubricating oil represented by Pennsylvania oil. In addition the oil is given an attractive green color and bloom characteristic of the highest grade oils.

As an example .of the operation'of my process and the production of my improved lubricating oils the following-is given. A

'"hard paraflin wax having a melting point of 122 to 125 F ischlorinated by the direct addition of chlorine in the presence of a trace of. iodi'neand at a temperature of about 200 F. The chlorine is blown through the oil for the temperature is raised gradually to about 200 F. The aluminuous sludge is then allowed to settle and the liquid oil is withdrawn and distilled to remove the kerosene and the unreacted paraflin as distillates. The heavy oil remaining has the following inspection:

Gravity '23.4 A. P. 1. Via. at 100 F 8500 see. Saybolt Vis. at 210 F 312 sec. Saybolt Pour 65 F. Flash 535 F. Conradson carbon 4.6%

Residual chlorine .27

A vacuum distilled Mid-Continent oil has the following inspection Gravity 24.7 A. P. I. Vis. at 100 F 981 sec. Saybolt Vis. at 210 F; I 79.3 sec. Saybolt Flash 515 F. Pour 35 F. Carbon .409%

A blend is then madeupsof 90% of the vacuum distilled Mid-Continent lubricating oil and 10% of the synthetic oil and the inspec- =t1on of the blend s as followsz- Gravity 245 A. P. I. Vis. at 100 F 1077 see. Saybolt Vis. at 210 F 86 sec. Saybolt Flash 515 F. Pour below... 10? Carbon 335% oil has been greatly reduced and the quality of the oil has been improved.

As a secondexample a distillate from Pennsylvania crude has the following characteristics:

Gravit 28.9 A. P. I.

Y Vis. at 100 F..... 433 sec. Sayholt Vis. at 210". F 60.5 sec,. Saybolt Flash 445 F. Pour above 30 F. Carbon 50% and is blended with 1% of asynthetic oil similar to that used in the firstexample and i the blend shows the-following inspection:

Gravit 28.8 A. P.'I. Vls. at 100.F- 450 sec. Saybolt Vis. at 210 F; 61.5 sec, Saybolt This blend d oil is found a be stable ever a long period of time, showing no separation or deterioration.

As a third example, Colombian lubri-' eating distillate after. treatment with 5 pounds of 66 B. sulphuric acid and having 105 It will be observed that the pour point of the been filtered with 5 pounds of day per barrel of oil has the following inspection:

Gravity 238 A. P. I. Vis. at 100 F 4 479 sec. Saybolt V15. at 210 F 56.5 sec. Saybolt Flash 410 F.

Pour 0 F.

"Carbon .152%

This oil is blended with synthetic oil Similar to that used in-Example 1, except that it had a viscosity of239 sec. Saybolt at 210 F. and a pour of 70 F. and with petrolatum of 31. A. P. I. gravity and having a viscosity of 43 sec. Saybolt at 210 F. The addition of the petrolatum causes the pour point of the Colombian oil and petrolatum mixture to be considerably higher than the Gravity 245 A. P. I. Vis. at 100 1 457 sec. Sayholt Vis. at 210 F 57.5 sec. Saybolt Pour below1 10 F. Carbon 347% Flash 410 1 with 1 part of the synthetic oil described in Example 1.- Inspections of the Colombian oil and the blend .is given below:

Hydrogenated Colombian oil Blend Gravity A. P. I Vise. at 100 F. (Saybolt).-. Vise. at 210 F. (Saybolt) Pour .below. Flash A particularly desirable feature of my invention comprises the use of narrow cut lubricating oils to be blended with the synthetic oil. These oils may be produced by fractionation or by ordinary vacuum distil- 1ation. Due to the narrow boiling range of the particular cut it is endowed with a relatively high flash in comparison with its Viscosity, and-if it is obtained from sweet crudes it is usually rich inparailin having a high pour point often above 50 F It is desirable to reduce the pour by the ordinary commercial methods, such as filtration to about 50 or preferably to 30 F. and to blend thereof with from 1 to- 5%of-the synthetic oil described; above. This'blend is particularly desirable in that it is found to have an abnormally high flash point for its viscosity at 210 FL and a pour. below 10 F. or even below zero.

As an example of this type of oil the following tests are given:

genate Colombian 1% blend oil Gravity A.P.I 27.4 27.3

Vis. at 100 F. (Saybolt). 495 500 Vis. at 210 F. (Saybolt) .1:

Pour 30 Below minus 20 F. 3 Flash 480 480 Boiling range 10 mm. of Hg 500-600 F.

This invention is not to be limited by any theory of the mechanism of the reactions, nor to any specific example which may have been given for the purpose of illustration,v but only by the following claims in which I wish to claim all novelty inherent in my invention.

I claim:

1. An improved lubricating oil comprising a blend of a viscous hydrocarbon fraction containing a solid waxy constituent in proportion sufficient to give a relatively high pour point and a synthetic hydrocarbon oil formed by the condensation of a waxy hydrocarbon material with an aromatic hydrocarbon.

2. A lubricating oil according to claim 1 in which the viscous hydrocarbon is a hydrogenated product.

3. An improved lubricating oil" comprising a blend of a heavy viscous hydrocarbon fraction containing a waxy constituent in proportion sufficient to give a relatively high pour point with a synthetic hydrocarbon oil obtained. by condensation of a waxy hydrocarbon with a. solid aromatic hydrocarbon, the synthetic oil being in pour reducing proportions only.

4. An improved lubricating oil with a pour point below 10 F. comprising ablend of a viscous hydrocarbon having a pour point above 30 F. with an efi'ective quantity of a synthetic hydrocarbon obtained by condensation 0 parafiin with an aromatic hydrocarbon.

5. An improved lubricating oil with a pour point below 0 F. comprising a blend of a viscous hydrocarbon having a pour point above 10 F. with an effective quantity of synthetic hydrocarbon obtained by condensation ofparafiin with an aromatic hydrocarbon. I

6. An improved lubricating oil of relatively low pour point comprising a blend of a petroleum fraction of relatively higher pour aromatic hydrocarbon, the synthetic oil being in pour reducing proportion, but below 10% and effective substantially only for pour reduction.

8. An improved lubricating oil of relatively low pour point comprising a blend of a petroleum fraction'of relatively higher pour point with a synthetic oil formed by the condensation of paraffin wax and a solid aromatic hydrocarbon, the synthetic oil being in pour reducing proportion, but below 5% and effective substantially only for pour reduction.

9. An improved lubricating oil of relatively low pour point comprising a blend of a petroleum fraction of relatively higher pour point with a synthetic oil formed by the condensation of paraffin Wax and a solid aromatic hydrocarbon, the synthetic oil being in pour reducing proportion, but below 1% and effective substantially only for pour reduction. a

10. An improved lubricating oil of relatively low pour point comprising a blend of a petroleum fraction of relatively higher pour point with a synthetic hydrocarbon oil in proportion effective for pour reduction only, the synthetic oil being a 10W temperatur'e aluminum chloride condensation'product of halogenatedparaffins and an aromatic hydrocarbon.

11. An improved lubricating oil of relatively low pour point comprising a-blend of a petroleum fraction of relatively higher pour point with a synthetic hydrocarbon oil in proportion'efiective for pour reduction only, the synthetic oil being a low tempera ture aluminum chloride condensation prod not of chlorinated paraifin Wax and naph-' thalene.

12. An improvedflubricating oil of relatively low pour point comprising a blend of a petroleum fraction of relatively-higher pour point with asynthetic hydrocarbon oil in proportion effective for pour reduction only,

the synthetic-oil being a low temperature, aluminum chloride condensation product of mono-chlor paraffin Wax and naphthalene.

13. An improved lubricating oil of low pour point comprising-a hydrocarbon oil of higher pour point'with a synthetichydrocarbon in an eifective proportion of the order of 1%, the synthetic 011 being a low temperature, aluminum chloride condensation prodnot of mono-.chlorparaifin,waxand naphthalene.

14. An improved lubricating oil of relatively low pour point comprising a viscous petroleum hydrocarbon of relatively higher pour point with'a synthetic hydrocarbon in 5 an effective proportion of the orderof 1%,

the synthetic oil beingv a low temperature,- aluminum chloride condensatio n'prodilct of mono-chlor paraflin Wax and naphthalene.

GARLAND H. B. DAVIS.- 

